JP6470545B2 - Ultra-low melting toner containing a crystalline diester containing an aromatic core - Google Patents

Description

  Embodiments disclosed herein generally relate to toner compositions that include a crystalline diester that includes an aromatic core. More specifically, embodiments disclosed herein relate to a toner composition that includes a low molecular crystalline aromatic diester compound that is compatible with the toner binder resin and that provides a low wrinkle fixing minimum fusing temperature.

  Electrophotography is a method for visualizing image information by creating an electrostatic latent image, and is currently used in various fields. The term “electrophotography” is generally used interchangeably with the term “electrophotography”. In general, electrophotography involves creating an electrostatic latent image on a photoreceptor, followed by developing the image with toner containing a developer, and then transferring material (eg, paper or Transferring the image to a sheet) and fixing the image to the transfer material by utilizing heat, solvent, pressure and / or the like to obtain a permanent image.

  Wrinkle fixed minimum fusing temperature (MFT) is an index used to determine the performance and energy efficiency of a specific toner in combination with a specific paper type and a specific fuser (fixing toner on the paper). is there. The wrinkle-fixed MFT is measured by folding the paper across the filled area of the image and then rolling a predetermined mass across the folded area. It is also possible to fold the paper using a commercially available folding machine (for example, a Duplo D-590 paper folding machine). A plurality of paper sheets containing images fused at a wide range of fusing temperatures are prepared. Next, the paper sheet is spread out, and the toner deviated from the paper sheet is wiped off from the surface. A wrinkle area may be optically compared to a reference chart that provides a definition of acceptable levels of toner adhesion, or the wrinkle area may be quantitatively analyzed by computer image analysis. The smaller the area where toner is lost, the better the toner adhesion, and the temperature required to achieve an acceptable level of adhesion is defined as wrinkle-fixed MFT.

  Currently, ultra-low melting point (ULM) emulsion aggregation (EA) toners have a wrinkle-fixing MFT as a reference of about −20 ° C. relative to styrene / acrylate EA toners. This improved wrinkle-fixing MFT performance can reduce fuser energy and improve fuser life when compared to EA toner. It is desired to lower the MFT by, for example, 10 ° C to 20 ° C.

  In some embodiments, a toner is provided comprising a polymer resin; optionally a colorant; and a low molecular crystalline diester comprising an aromatic core having a molecular weight of less than 1,000 g / mol.

  Another embodiment comprises an amorphous polymer resin; optionally a colorant; and a low molecular crystalline diester comprising an aromatic core having a molecular weight of less than 500 g / mol and a melting point of about 60 ° C. to about 120 ° C. A mixture of amorphous polymer resin and low molecular crystalline aromatic diester has a lower glass transition temperature than amorphous polymer resin, as determined by differential scanning calorimetry, and low molecular crystalline aromatic diester solid to liquid There is no significant phase transition peak to, and the fusion enthalpy of the low molecular crystalline aromatic diester in the mixture is measured to be less than 10% of the fusion enthalpy of the low molecular crystalline aromatic diester in pure form. An emulsion aggregation toner is provided.

  In yet another embodiment, it comprises a polymer amorphous resin emulsion, optionally at least one colorant emulsion, an optional wax emulsion, a low molecular crystalline aromatic diester emulsion, an aromatic core having a molecular weight of less than 1,000 g / mol. There is provided a method for producing toner particles comprising mixing a low molecular crystalline diester to form a composite emulsion; and adding an aggregating agent to the composite emulsion to form an emulsion aggregated toner particle.

FIG. 1 is a differential scanning calorimetry (DSC) curve of melt mixed di-tert-butylisophthalate and amorphous polyester resin. FIG. 2 is a DSC curve of melt mixed isophthalic acid, diphenyl ester and amorphous polyester resin. FIG. 3 is a DSC curve of melt mixed terephthalic acid, distearyl ester and amorphous polyester resin.

  According to the present disclosure, a toner comprising a low molecular crystalline diester comprising an aromatic core is provided. In some embodiments, the toner may include a low molecular crystalline diester that includes an aromatic core and an amorphous polymer resin, and the mixture of the amorphous polymer resin and the low molecular crystalline aromatic diester includes a differential scanning calorific value. As determined by measurement, the glass transition temperature is lower than that of the amorphous polymer resin, and there is no significant phase transition peak from solid to liquid of the low molecular crystalline aromatic diester. For example, the absence of a noticeable phase transition peak from solid to liquid indicates that the fusion enthalpy of the low molecular crystalline aromatic diester in the mixture is less than 20% of its original value of fusion enthalpy, in some embodiments May be indicated by being measured to be less than 10% of its original value, and in some embodiments less than 5% of its original value, the original value when measured independently Represents the low molecular fusion enthalpy, which characterizes the compatibility of low molecular crystalline aromatic diesters with amorphous polymer resins. Further, in some embodiments, the low molecular crystalline aromatic diester may have a melting point of less than 120 ° C. According to certain embodiments, an emulsion aggregation (EA) toner comprising a low molecular crystalline diester comprising an aromatic core is a nominal ULM EA toner, such as Xerox Corp. Will achieve at least comparable wrinkle-fixed MFT, for example, at least 5 ° C., or at least 10 ° C. to 20 ° C. lower than the Xerox® 700 Digital Color Press (DCP) toner available from .

  Any toner resin may be utilized in the disclosed process. As such, such resins may be made from any suitable one or more monomers by any suitable polymerization method. In some embodiments, the resin may be prepared by methods other than emulsion polymerization. In a further embodiment, the resin may be prepared by condensation polymerization.

  In some embodiments, the resin may be polyester, polyimide, polyolefin, polyamide, polycarbonate, epoxy resin, and / or copolymers thereof. In some embodiments, the resin may be an amorphous resin, a crystalline resin, and / or a mixture of a crystalline resin and an amorphous resin. The crystalline resin may be present in the mixture of crystalline resin and amorphous resin, for example, in an amount of 0 to about 50% by weight of the total toner resin, and in some embodiments 5 to about 35% by weight. Good. The amorphous resin may be present in the mixture, for example, in an amount of about 50 to about 100% by weight of the total toner resin, and in some embodiments 95 to about 65% by weight.

  In some embodiments, the amorphous resin may be selected from the group consisting of polyester, polyamide, polyimide, polystyrene-acrylate, polystyrene-methacrylate, polystyrene-butadiene, or polyester-imide, and mixtures thereof. In some embodiments, the crystalline resin is selected from the group consisting of polyester, polyamide, polyimide, polyethylene, polypropylene, polybutylene, polyisobutyrate, ethylene-propylene copolymer, or ethylene-vinyl acetate copolymer, and mixtures thereof. May be. In a further embodiment, the resin may be a polyester crystalline resin and / or a polyester amorphous resin. In some embodiments, the polymer utilized to make the resin may be a polyester resin including the resins described in US Pat. Nos. 6,593,049 and 6,756,176. . Suitable resins may also include a mixture of amorphous polyester resin and crystalline polyester resin as described in US Pat. No. 6,830,860.

  In some embodiments, the resin may be a polyester resin made by reacting a diol with a diacid in the presence of an optional catalyst. For making crystalline polyesters, suitable organic diols include aliphatic diols containing from about 2 to about 36 carbon atoms, such as 1,2-ethanediol, 1,3-propanediol, 1,4 -Butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12- Examples include dodecanediol and combinations thereof. The aliphatic diol is, for example, in an amount of about 40 to about 60 mol% of the resin, in some embodiments about 42 to about 55 mol%, and in some embodiments about 45 to about 53 mol%. May be selected.

  Examples of organic diacids or diesters selected to prepare crystalline resins include oxalic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, fumaric acid, maleic acid, dodecanedioic acid, sebacine Acid, phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, cyclohexanedicarboxylic acid, malonic acid and mesaconic acid, their diesters or acid anhydrides, and these Combinations are listed. The organic diacid is, for example, from about 40 to about 60 mole percent in some embodiments, from about 42 to about 55 mole percent in some embodiments, and from about 45 to about 53 moles in some embodiments. % Amount may be selected.

  Examples of the crystalline resin include polyester, polyamide, polyimide, polyolefin, polyethylene, polybutylene, polyisobutyrate, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, polypropylene, and a mixture thereof. Specific crystalline resins include polyesters such as poly (ethylene-adipate), poly (propylene-adipate), poly (butylene-adipate), poly (pentylene-adipate), poly (hexylene-adipate), poly ( Octylene-adipate), poly (ethylene-succinate), poly (propylene-succinate), poly (butylene-succinate), poly (pentylene-succinate), poly (hexylene-succinate), poly (octylene-succinate), poly (ethylene) -Sebacate), poly (propylene-sebacate), poly (butylene-sebacate), poly (pentylene-sebacate), poly (hexylene-sebacate), poly (octylene-sebacate), alkali copoly (5-sulfoisophthaloyl)- Poly (ethylene-adipate), poly (decylene-sebacate), poly (decylene-decanedioate), poly- (ethylene-decanedioate), poly- (ethylene-dodecanedioate), poly (nonylene-sebacate), Poly (nonylene-decanedioate), poly (nonylene-dodecanedioate), poly (decylene-dodecanedioate), copoly (ethylene-fumarate) -copoly (ethylene-sebacate), copoly (ethylene-fumarate) -copoly ( It may be ethylene-decanedioate) and copoly (ethylene-fumarate) -copoly (ethylene-dodecanedioate). When utilized, the crystalline resin is present, for example, in an amount of about 5 to about 50% by weight of the toner element, and in some embodiments, about 10 to about 35% by weight of the toner element. Also good.

  The crystalline resin may have various melting points, for example, the melting point may be 30 ° C. to 120 ° C., and in some embodiments, about 50 ° C. to about 90 ° C. The crystalline resin has a number average molecular weight (Mn) of, for example, from about 1,000 to about 50,000, in some embodiments from about 2,000 to about 50,000, as measured by gel permeation chromatography (GPC). 25,000, and when the weight average molecular weight (Mw) is determined by gel permeation chromatography using polystyrene standards, for example, from about 2,000 to about 100,000, in some embodiments, About 3,000 to about 80,000 may be used. The molecular weight distribution (Mw / Mn) of the crystalline resin may be, for example, from about 2 to about 6, and in some embodiments from about 2 to about 4.

  Examples of diacids or diesters selected to prepare amorphous polyesters include dicarboxylic acids or diesters such as terephthalic acid, phthalic acid, isophthalic acid, fumaric acid, maleic acid, succinic acid, itaconic acid, succinic acid, Succinic anhydride, dodecenyl succinic acid, dodecenyl succinic anhydride, glutaric acid, glutaric anhydride, adipic acid, pimelic acid, suberic acid, azelaic acid, dodecanedioic acid, dimethyl terephthalate, diethyl terephthalate, dimethyl isophthalate, diethyl isophthalate, Dimethyl phthalate, phthalic anhydride, diethyl phthalate, dimethyl succinate, dimethyl fumarate, dimethyl maleate, dimethyl glutarate, dimethyl adipate, dimethyl dodecenyl succinate, and combinations thereof. The organic diacid or diester is, for example, from about 40 to about 60 mole percent of the resin, in some embodiments, from about 42 to about 55 mole percent of the resin, in some embodiments, from about 45 to about 53 of the resin. It may be present in an amount of mol%.

  Examples of diols utilized in making amorphous polyesters include 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol , Pentanediol, hexanediol, 2,2-dimethylpropanediol, 2,2,3-trimethylhexanediol, heptanediol, dodecanediol, bis (hydroxyethyl) -bisphenol A, bis (2-hydroxypropyl) -bisphenol A 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, xylenedimethanol, cyclohexanediol, diethylene glycol, bis (2-hydroxyethyl) oxide, dipropylene glycol, dibutylene glycol, and The combination of these, and the like. The amount of organic diol selected may vary, for example, from about 40 to about 60 mole percent of the resin, in some embodiments, from about 42 to about 55 mole percent of the resin, in some embodiments. Then, it may be present in an amount of about 45 to about 53 mole percent of the resin.

  In some embodiments, a polycondensation catalyst may be used when making the polyester. Polycondensation catalysts that can be utilized in either crystalline or amorphous polyesters include tetraalkyl titanates, dialkyltin oxides (eg, dibutyltin oxide), tetraalkyltins (eg, dibutyltin dilaurate), dialkyltin oxide hydroxides (Eg, butyltin oxide hydroxide, tin octoate), aluminum alkoxide, alkyl zinc, dialkyl zinc, zinc oxide, stannous oxide, or combinations thereof. Such catalysts may be utilized in amounts of, for example, from about 0.01 mol% to about 5 mol%, based on the starting diacid or diester used to make the polyester resin.

  In some embodiments, suitable amorphous resins include polyester, polyamide, polyimide, polyolefin, polyethylene, polybutylene, polyisobutyrate, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, polypropylene, combinations thereof, and the like. It is done. Examples of available amorphous resins include alkali sulfonated-polyester resins, branched-chain alkali sulfonated-polyester resins, alkali-sulfonated-polyimide resins, and branched-chain alkaline sulfonated-polyimide resins. Alkaline sulfonated polyester resins may be useful, and in some embodiments, for example, copoly (ethylene-terephthalate) -copoly (ethylene-5-sulfo-isophthalate), copoly (propylene-terephthalate) -copoly ( Propylene-5-sulfo-isophthalate), copoly (diethylene-terephthalate) -copoly (diethylene-5-sulfoisophthalate), copoly (propylene-diethylene-terephthalate) -copoly (propylene-diethylene-5-sulfoisophthalate), Copoly (propylene-butylene-terephthalate) -copoly (propylene-butylene-5-sulfoisophthalate) and copoly (propoxylated bisphenol A-fumarate) -copoly (propoxylated bisphenol A-5) Sulfo - isophthalate) may be a metal salt or an alkali salt.

  In some embodiments, an unsaturated amorphous polyester resin may be utilized as the latex resin. Examples of such resins include those disclosed in US Pat. No. 6,063,827. Exemplary unsaturated amorphous polyester resins include, but are not limited to, poly (propoxylated bisphenol cofumarate), poly (ethoxylated bisphenol cofumarate), poly (butyloxylated bisphenol cofumarate), poly (copolymer). -Propoxylated bisphenol co-ethoxylated bisphenol co-fumarate), poly (1,2-propylene fumarate), poly (propoxylated bisphenol co-maleate), poly (ethoxylated bisphenol co-maleate), poly (butyl Oxylated bisphenol co-maleate), poly (co-propoxylated bisphenol co-ethoxylated bisphenol co-maleate), poly (1,2-propylene maleate), poly (propoxylated bis Enol co-itaconate), poly (ethoxylated bisphenol co-itaconate), poly (butyloxylated bisphenol co-itaconate), poly (co-propoxylated bisphenol co-ethoxylated bisphenol co-itaconate), poly (1,2 -Propylene itaconate), and combinations thereof.

Amorphous resins have various glass transition temperatures (Tg) of, for example, about 40 ° C. to about 100 ° C., in some embodiments, about 45 ° C. to about 70 ° C., and in some embodiments, 50 ° C. to about 65 ° C. It may be. The crystalline resin has a number average molecular weight ( _Mn ) of, for example, about 1,000 to about 50,000, in some embodiments, about 2,000 to about 25,000, and in some embodiments about 2 From about 2,000 to about 100,000 when the weight average molecular weight (M _w ) is determined by gel permeation chromatography (GPC) using polystyrene standards. , In some embodiments, from about 3,000 to about 80,000, and in some embodiments, from about 4,000 to about 20,000. The molecular weight distribution (M _w / M _n ) of the crystalline resin may be, for example, from about 2 to about 6, in some embodiments from about 2 to about 5, and in some embodiments from about 2 to about 4. Good.

For example, in some embodiments, the amorphous polyester resin may be a poly (propoxylated bisphenol A co-fumarate) resin having the following formula (1):
Wherein m may be from about 5 to about 1000, in some embodiments from about 10 to about 500, and in other embodiments from about 15 to about 200. Examples of such resins and their manufacturing processes include those disclosed in US Pat. No. 6,063,827.

  An example of a linear propoxylated bisphenol A fumarate resin that can be used as a toner resin is available from Resana S / A Industries Quimicas (São Paulo, Brazil) under the trade name SPARII. Other propoxylated bisphenol A fumarate resins that are available and commercially available include GTUF and FPESL-2, Reichhold, Research Triangle Park, Kaolin Corporation (Japan), and EM181635 from North Carolina.

  In some embodiments, the amorphous polyester resin may be a copolymer of alkoxylated bisphenol A and at least one diacid. The alkoxylated bisphenol A may comprise ethoxylated bisphenol A, propoxylated bisphenol A, and / or ethoxylated-propoxylated bisphenol A. Suitable diacids include fumaric acid, terephthalic acid, dodecenyl succinic acid, and / or trimellitic acid.

  In some embodiments, a combination of low and high Mw amorphous resin may be used to make the toner. The low Mw resin may have a weight average molecular weight of about 10 kg / mol to about 20 kg / mol, and a number average molecular weight of about 2 kg / mol to about 5 kg / mol. The high Mw resin may have a weight average molecular weight of about 90 kg / mol to about 160 kg / mol, and a number average molecular weight of about 4 kg / mol to about 8 kg / mol. The weight ratio of low Mw amorphous resin to high Mw amorphous resin is about 0: 100 to about 100: 0, in some embodiments, about 70:30 to about 30:70, and in some embodiments, about 60:40. May be about 40:60.

Further examples of crystalline resins that can be used in combination with the amorphous resin as described above include those disclosed in US Patent Publication No. 2006/0222991. In some embodiments, a suitable crystalline resin may include a resin made from ethylene glycol having the following formula (2) and a mixture of dodecanedioic acid and fumaric acid comonomer:
Where b is from about 5 to about 2000 and d is from about 5 to about 2000.

  For example, in some embodiments, a poly (propoxylated bisphenol A cofumarate) resin of formula I as described above is combined with a crystalline resin of formula II to make a resin suitable for making a toner. May be created.

  Examples of other toner resins or polymers that can be utilized include those derived from styrene, acrylate, methacrylate, butadiene, isoprene, acrylic acid, methacrylic acid, acrylonitrile, and combinations thereof. Exemplary additional resins or polymers include, but are not limited to, poly (styrene-butadiene), poly (methylstyrene-butadiene), poly (methyl methacrylate-butadiene), poly (ethyl methacrylate-butadiene), poly (methacrylic). Propyl butadiene), poly (butyl methacrylate-butadiene), poly (methyl acrylate-butadiene), poly (ethyl acrylate-butadiene), poly (propyl acrylate-butadiene), poly (butyl acrylate-butadiene) , Poly (styrene-isoprene), poly (methylstyrene-isoprene), poly (methyl methacrylate-isoprene), poly (ethyl methacrylate-isoprene), poly (propyl methacrylate-isoprene), poly (butyl methacrylate-isoprene) , Poly (methyl acrylate-isoprene), poly (ethyl acrylate-isoprene), poly (propyl acrylate-isoprene), poly (butyl acrylate-isoprene); poly (styrene-propyl acrylate), poly (styrene- Butyl acrylate), poly (styrene-butadiene-acrylic acid), poly (styrene-butadiene-methacrylic acid), poly (styrene-butadiene-acrylonitrile-acrylic acid), poly (styrene-butyl acrylate-acrylic acid), poly (Styrene-butyl acrylate-methacrylic acid), poly (styrene-butyl acrylate-acrylonitrile) and poly (styrene-butyl acrylate-acrylonitrile-acrylic acid), and combinations thereof. The polymer may be a block copolymer, a random copolymer or an alternating copolymer.

In a further embodiment, the resin utilized in the toner has a melt viscosity at about 130 ° C. of about 10 to about 1,000,000 Pascal second (Pa ^* s), in some embodiments about 20 to about It may be 100,000 Pa ^* s.

  One, two, or more types of toner resins may be used. In embodiments using more than one toner resin, the toner resin may be in any suitable ratio (eg, weight ratio), for example, about 10% (first resin) / 90% (first 2 resin) to about 90% (first resin) / 10% (second resin).

  In some embodiments, the polymer latex may be made by an emulsification method. Utilizing such methods, the resin may be present in the resin emulsion, which may then be combined with other elements and additives to make the toner of the present disclosure.

  The polymer resin is about 65 to about 95% by weight of toner particles (ie, toner particles excluding external additives) on a solids basis, in some embodiments about 70 to about 90% by weight, and in some embodiments It may be present in an amount of about 75 to about 85% by weight. Where the resin is a combination of a crystalline resin and one or more amorphous resins, the ratio of crystalline resin to amorphous resin in some embodiments is about 1:99 to about 30:70, in some embodiments. From about 5:95 to about 25:75, and in some embodiments from about 5:95 to about 15:85.

  In some embodiments, the resin, colorant, wax, and other additives utilized to make the toner composition may be in the form of a dispersant including a surfactant. In addition, the toner particles can be collected by placing the resin and other components of the toner in one or more surfactants, creating an emulsion, agglomerating and fusing the toner particles, and optionally washing, drying, and collecting. It may be prepared by an emulsion aggregation method.

  One, two, or more surfactants may be utilized. The surfactant may be selected from ionic surfactants and nonionic surfactants. Anionic surfactants and cationic surfactants are encompassed by the term “ionic surfactant”. In some embodiments, the surfactant is about 0.01% to about 5% by weight of the toner composition, such as about 0.75% to about 4%, and in some embodiments about It may be utilized to be present in an amount of 1% to about 3% by weight.

  Examples of usable nonionic surfactants include, for example, polyacrylic acid, metalose, methylcellulose, ethylcellulose, propylcellulose, hydroxyethylcellulose, carboxymethylcellulose, polyoxyethylene cetyl ether, polyoxyethylene lauryl ether, polyoxyethylene Octyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitan monolaurate, polyoxyethylene stearyl ether, polyoxyethylene nonylphenyl ether, dialkylphenoxy poly (ethyleneoxy) ethanol (from Rhone-Poulenc) IGEPAL CA-210 (trademark), IGEPAL CA-520 (trademark), IGEPA L CA-720 (TM), IGEPAL CO-890 (TM), IGEPAL CO-720 (TM), IGEPAL CO-290 (TM), IGEPAL CA-210 (TM), ANTAROX 890 (TM) and ANTAROX 897 (TM) ) Is available). Other examples of suitable nonionic surfactants include block copolymers of polyethylene oxide and polypropylene oxide, such as SYNPERONIC ™ PE / F, and in some embodiments, SYNPERONIC ™ PE / F 108. Are commercially available.

  Available anionic surfactants include sulfates and sulfonates, sodium dodecyl sulfate (SDS), sodium dodecylbenzene sulfonate, sodium dodecyl naphthalene sulfate, dialkylbenzene alkyl sulfates and sulfonates, acids such as abietics available from Aldrich Acid, NEOGEN R (trademark) available from Daiichi Kogyo Co., Ltd., NEOGEN SC (trademark), combinations thereof and the like. Other suitable anionic surfactants include, in some embodiments, alkyl diphenyl oxide disulfonate DOWFAX ™ 2A1 from The Dow Chemical Company, and / or branched sodium from Tayca Corporation (Japan). Dodecylbenzenesulfonate TAYCA POWER BN2060. In some embodiments, combinations of these surfactants with any of the above-described anionic surfactants may be utilized.

Examples of cationic surfactants that are normally positively charged include, for example, alkylbenzyldimethylammonium chloride, dialkylbenzenealkylammonium chloride, lauryltrimethylammonium chloride, alkylbenzylmethylammonium chloride, alkylbenzyldimethylammonium bromide, benza. Luconium chloride, cetylpyridinium bromide, C ₁₂ , C ₁₅ , C ₁₇ trimethylammonium bromide, quaternized polyoxyethylalkylamine halide salt, dodecylbenzyltriethylammonium chloride, MIRAPOL ™ and ALKAQUAT ™ ( Available from Alcaril Chemical Company), SAN available from Kao Chemicals Such ZOL (TM) (benzalkonium chloride), and the like and mixtures thereof.

  As optional optional colorants to be added, various known suitable colorants such as dyes, pigments, dye mixtures, pigment mixtures, dye and pigment mixtures and the like may be included in the toner. The colorant is included in the toner, for example, in an amount of about 0.1 to about 35% by weight of the toner, or about 1 to about 15% by weight of the toner, or about 3 to about 10% by weight of the toner. Also good.

  Examples of suitable colorants include carbon black such as REGAL 330®; Mobay magnetite such as magnetite, MO8029 ™, MO8060 ™; Columbian magnetite; MAPICO BLACKS ™ and surface treated magnetite CB4799 (trademark), CB5300 (trademark), CB5600 (trademark), MCX6369 (trademark) and other Pfizer magnetites; BAYFERROX 8600 (trademark), 8610 (trademark) and other Bayer magnetites; NP604 (trademark), NP608 (trademark), etc. North Pigment magnetite of the company; Magnox magnetite such as TMB-100 ™ or TMB-104 ™. The colored pigment may be selected from cyan, magenta, yellow, red, green, brown, blue, or mixtures thereof. In general, cyan, magenta or yellow pigments or dyes or mixtures thereof are used. One or more pigments are generally used as the aqueous pigment dispersion.

  Specific examples of pigments include SUNSPERSE 6000, FLEXIVESE and AQUATONE aqueous pigment dispersions, HELIOGEN BLUE L6900 (trademark), D6840 (trademark), D7080 (trademark), D7020 (trademark), PYLAM OIL BLUE (trademark) manufactured by SUN Chemicals. , PYLAM OIL YELLOW (TM), PIGMENT BLUE 1 (TM) (available from Paul Uhrich & Company, Inc.), PIGMENT VIOLET 1 (TM), PIMMENT RED 48 (TM), LEMON CHROME YELLOW DCE 1026 D. TOLUIDINE RED (TM) and BON RED C (TM) (available from Dominion Color Corporation, Ltd. (Toronto, Ontario)), NOVAPERM YELLOW FGL (TM), HOSTAPER PINK ET (from Hoechst) and CINQUASIAMA trademark EI DuPont de Nemours & Company). In general, selectable colorants are black, cyan, magenta or yellow, and mixtures thereof. Examples of magenta are 2,9-dimethyl-substituted quinacridone and anthraquinone dyes identified as CI 60710 by Color Index, CI Dispersed Red 15, CI Dissolved Red 19, which are diazo dyes identified as CI 26050 by Color Index, and the like. is there. Specific examples of cyan include copper tetra (octadecylsulfonamide) phthalocyanine, x-copper phthalocyanine pigment identified as Cl 74160 in Color Index, CI Pigment Blue, Pigment Blue 15: 3, identified as Cl 69810 in Color Index. Anthracene Blue, Special Blue X-2137 and the like. Specific examples of yellow are diarylide yellow 3,3-dichlorobenzideneacetoacetanilide, monoazo pigment identified as Cl 12700 by Color Index, nitro identified as Cl Solvent Yellow 16, Foron Yellow SE / GLN by Color Index Phenylaminesulfonamide, Cl Dispersed Yellow 33, 2,5-dimethoxy-4-sulfonanilide phenylazo-4′-chloro-2,5-dimethoxyacetoacetanilide, Permanent Yellow FGL. Colored magnetite (eg, a mixture of MAPICO BLACK ™ and cyan component) may be selected as the colorant. For example, Levanyl Black A-SF (Miles, Bayer) and Sunsperse Carbon Black LHD 9303 (Sun Chemicals) and colored dyes such as Neopen Blue (BASF), Sudan Blue OS (BASF), , Sunsperse Blue BHD 6000 (Sun Chemicals), Irgalite Blue BCA (Ciba-Geigy), Palogen Blue 6470 (BASF), Sudan III (Matheson, Coleman, Bell), Sule III (Matheon, Coleman, Bell) atheson, Coleman, Bell), Sudan Orange G (Aldrich), Sudan Orange 220 (BASF), Paligen Orange 3040 (BASF), Ortho Orange OR 2673 (Paul UHrich), Pell UBrich, 15 (BASF), Pariotool Yellow 1840 (BASF), Neopen Yellow (BASF), Novoperm Yellow FG 1 (Hoechst), Permanent Yellow YE 0305 (Paul Uhrich), Lumogen 0S 90 e Yellow YHD 6001 (Sun Chemicals), Suco-Gel L1250 (BASF), Suco-Yellow D1355 (BASF), Hostaper Pink E (American Hoechst), Fanal Pink D4830 (BASt) BASF), Toluidine Red (Aldrich), Scallet for Thermoplast NSD PS PA (Ugin Kuhlmann of Canada), E.I. D. Toluidine Red (Aldrich), Lithol Ruby Toner (Paul Uhrich), Lithol Scallet 4440 (BASF), Bon Red C (Dominion Color Company), Royal Brilliant Red RD 8192C (ul) Other known colorants may be selected, such as Palogen Red 3871K (BASF), Palogen Red 3340 (BASF), Lithol Fast Scallet L4300 (BASF), combinations of the above.

  Optionally, the wax may be combined with a resin and an optional colorant when making the toner particles. When included, the wax is present, for example, in an amount from about 1% to about 25% by weight of the toner particles, and in some embodiments from about 5% to about 20% by weight of the toner particles. Also good.

  Selectable waxes include, for example, waxes having a weight average molecular weight (Mw) of about 500 to about 20,000, and in some embodiments, about 1,000 to about 10,000. Usable waxes include, for example, polyolefins such as polyethylene, polypropylene and polybutene waxes, such as those commercially available from Allied Chemical and Petrolite Corporation, such as POLYWAX ™ polyethylene wax from Baker Petrolite, Michaelman, Inc. . And wax emulsions from Daniels Products Company, Eastman Chemical Products, Inc. EPOLENE N-15 (trademark) available from Sanyo Chemical Industries, Ltd .; low weight average molecular weight polypropylene VISCOL 550-P (trademark) available from Sanyo Chemical Industries; plant waxes such as carnauba wax, rice bran, candelilla wax, Japanese Wax, jojoba oil; animal waxes such as beeswax; mineral waxes and petroleum waxes such as montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax and Fischer-Tropsch wax; obtained from higher fatty acids and higher alcohols Ester waxes such as stearyl stearate and behenyl behenate; ester waxes derived from higher fatty acids and mono- or polyhydric lower alcohols such as butyl stearate, propyl oleate, glycerides Seride monostearate, glyceride distearate and pentaerythritol tetrabehenate; ester waxes derived from higher fatty acids and polyhydric alcohol multimers such as diethylene glycol monostearate, dipropylene glycol distearate, diglyceryl distearate And triglyceryl tetrastearate; sorbitan higher fatty acid ester waxes such as sorbitan monostearate and cholesterol higher fatty acid ester waxes such as cholesteryl stearate. Examples of functionalized waxes that can be used include, for example, amines, amides, such as Micro Powder Inc. AQUA SUPERSLIP 6550 ™, SUPERSLIP 6530 ™, fluorinated waxes such as Micro Powder Inc. available from POLYFLUO 190 (TM), POLYFLUO 200 (TM), POLYSILK 19 (TM), POLYSILK 14 (TM), mixed and fluorinated, amide waxes, such as Micro Powder Inc. MICROSPERSION 19 ™, imides, esters, quaternary amines, carboxylic acid or acrylic polymer emulsions available from, for example, JONCRYL 74 ™, 89 ™, 130 ™, 537 ™ and 538 ( (Trademark) (all available from SC Johnson Wax), chlorinated polypropylene and polyethylene available from Allied Chemical and Petrolite Corporation, and SC Johnson Wax. In some embodiments, mixtures and combinations of the above waxes may also be used. Wax may be included as a fuser roll release agent, for example.

  In some embodiments, a shell may be applied to the resulting aggregated toner particles. Any resin described above as suitable for the core resin can be used as the shell resin. The shell resin may be applied to the aggregated particles by any method within the skill of the art. In some embodiments, the shell resin may be in the form of an emulsion that includes any of the surfactants described above. The agglomerated particles described above may be combined with the above shell resin emulsion so that the shell resin forms a shell on the resulting agglomerates. In some embodiments, at least one amorphous polyester resin may be utilized to create a shell on the agglomerate to produce toner particles having a core-shell structure. In some embodiments, an amorphous polyester resin and a crystalline resin may be utilized to create a shell on the agglomerate to produce toner particles having a core-shell structure. In some embodiments, a suitable shell is from about 10% to about 90% by weight of the shell, in some embodiments, from about 20% to about 80% by weight of the shell, in some embodiments, It may comprise at least one amorphous polyester resin present in an amount from about 30% to about 70% by weight of the shell.

  The shell resin may be present in an amount from about 5% to about 40% by weight of the toner particles, and in some embodiments from about 24% to about 30% by weight of the toner particles.

  Once the desired final particle size of the toner particles is reached, a base may be used to adjust the pH of the mixture to a value of about 5 to about 10, and in some embodiments, about 6 to about 8. Adjustment of pH may be utilized to freeze (ie, stop) toner growth. Bases utilized to stop toner growth include any suitable base, such as alkali metal hydroxides (eg, sodium hydroxide, potassium hydroxide, ammonium hydroxide, combinations thereof, etc.). Can do. The base may be added in an amount of about 2 to about 25% by weight of the mixture, and in some embodiments about 4 to about 10% by weight of the mixture. In addition, the addition of EDTA solution may be used to freeze shell growth. In some embodiments, a combination of EDTA and base solutions may be used to freeze toner particle growth.

  In some embodiments, a low molecular crystalline aromatic diester compound that is a crystalline solid at room temperature is added to the toner to lower the minimum fusion temperature (MFT) of the toner. In a specific embodiment, when the low molecular crystalline aromatic diester compound is added to an emulsion aggregation (EA) toner and completely or partially replaced with a crystalline polymer element, the low molecular crystalline organic compound is It is compatible with the toner amorphous binder resin. Compatibility may be demonstrated by characterizing a molten mixture of an amorphous resin and a low molecular crystalline aromatic diester compound, the molten mixture being glass rather than an amorphous resin, as determined by differential scanning calorimetry. The transition enthalpy of the low molecular crystalline aromatic diester compound in the mixture is low, the transition enthalpy of the low molecular crystalline aromatic diester compound in the mixture is low Less than 10% of its original value, in some embodiments, less than 5% of its original value, and in some embodiments, this original value is measured independently. The low molecular fusion enthalpy of the amorphous resin and the low molecular crystalline aromatic diester compound, It is considered to be soluble. Further, in some embodiments, the low molecular crystalline aromatic diester compound has a melting point that is lower than the fusion temperature of the EA toner. According to certain embodiments, an emulsion aggregation toner comprising a low molecular crystalline aromatic diester compound is a nominal ULM toner, such as Xerox Corp. For example, at least comparable wrinkle-fixed MFT will be achieved, if not at least 5 ° C., or at least 10 ° C. to 20 ° C. lower than the Xerox® 700 DCP toner available from

  In some embodiments, the low molecular crystalline aromatic diester compound has a molecular weight of less than 1,000 g / mol; in a further embodiment, the low molecular crystalline aromatic diester compound has a molecular weight of less than 750 g / mol; In yet a further embodiment, the low molecular crystalline aromatic diester compound has a molecular weight of less than 500 g / mol.

  Briefly, the compatibility test for an amorphous resin and a low molecular crystalline aromatic diester compound proceeds as follows. The low molecular crystalline aromatic diester compound is mixed with the amorphous resin at a ratio similar to that of the toner itself. The mixture is heated to a temperature at least above the melting point of the crystalline element with sufficient time to melt completely while mixing and then cooled to room temperature. The resulting material is analyzed by DSC. In this test, it is believed that, as it cools, low molecules that are not compatible with the resin will recrystallize from the molten mixture, and the resulting DSC trajectory is: (1) a clear melting peak corresponding to the low molecules; (2) The original glass transition of the amorphous resin (which may or may not be shifted to a slightly lower temperature). When incorporated into EA toners, small molecules having this characteristic generally do not provide low melt toner properties. In contrast, small molecules that are compatible with the resin generally do not recrystallize from the molten mixture. In these cases, the resulting DSC trajectory shows (1) a weak or completely absent melt transition, (2) a weakened and / or shifted glass transition, which is low It shows the plasticization of amorphous resin by molecules. When incorporated into EA toners, these small molecules generally provide low melt properties, and the melting point of the low molecules is lower than the typical fusing temperature of the toner (typical ULM EA toners such as Xerox ( (Registered trademark) 700 DCP toner, about 110 ° C. to 120 ° C.). Furthermore, to measure the degree of compatibility, the crystallization enthalpy may be measured, and in the case of perfect compatibility, a value of less than 5% of the original value is obtained, while completely incompatible In some cases, a value greater than 20% of the original value is obtained, which represents the fusion enthalpy of the small molecule when measured independently.

Examples of suitable aromatic diesters include those of formulas 3, 4, and 5
In the formula, R ₁ and R ₂ may be the same or different. In some embodiments, R ₁ and R ₂ may be selected from the group consisting of aryl groups, alkyl groups, aryl-alkyl groups, alkyl-aryl groups. In certain embodiments, the aromatic diester has a carbon to oxygen ratio of 3.5-6, similar to the carbon to oxygen ratio of the resin used in the toner. The thermal properties of these aromatic diesters are given in Table 1 for the specific examples of R ₁ and R ₂ .

In certain embodiments, the aromatic diester is di-tert-butyl isophthalate of formula (6) (ratio to oxygen, melting point 83 ° C.).

  Toner particles may be prepared by any method within the common general knowledge of the art. Embodiments related to the production of toner particles are described below with respect to the emulsion aggregation process, but the chemical processes (eg, suspensions disclosed in US Pat. Nos. 5,290,654 and 5,302,486). Any suitable method of preparing toner particles may be used, including turbidity and encapsulation processes. In some embodiments, the toner composition is formed by an agglomeration fusing process in which low molecular resin particles are agglomerated to a suitable toner particle size and then fused to achieve the final toner particle shape and morphology. And toner particles may be prepared.

  In some embodiments, an emulsion aggregation process, such as an optional colorant, optional wax, and any other desirable or necessary additives, an emulsion comprising the resin described above, and at least one of the above described The toner composition may be prepared by a process comprising agglomerating a mixture optionally containing one or more low molecular crystalline aromatic diester compounds in the surfactant described above and then fusing the agglomerated mixture. . Examples of potentially suitable colorants, waxes and / or other additives are described above. In some embodiments, the low molecular crystalline aromatic diester compound is about 5% to about 25% of the dry weight of the toner without any external additives, and in some embodiments about 10% to about 20%. In some embodiments, the low molecular weight crystalline aromatic diester compound is about 15% of the dry weight of the toner. In some embodiments, an emulsion of each component is prepared and then combined together. Further, in some embodiments, the toner includes both a low molecular crystalline aromatic diester compound and a crystalline resin. For example, the crystalline resin may be the crystalline polyester resin described above and / or any other crystalline resin described herein. In some embodiments, the crystalline resin is about 3% to about 20% of the dry weight of the toner without any external additives, and in some embodiments, about 5% to about 15%. In form, the low molecular crystalline organic compound is about 5% to about 10% of the dry weight of the toner.

  Optional colorants, waxes and / or other materials (which may optionally be in the form of a dispersion containing a surfactant) may be an emulsion (a mixture of two or more emulsions containing a resin). The mixture may be prepared by adding to If necessary, the pH of the resulting mixture may be adjusted.

  After preparing the above mixture, a flocculant or flocculant may be added to the mixture. Any suitable flocculant may be utilized to make the toner. Suitable flocculants include, for example, divalent cation materials or aqueous solutions of polyvalent cation materials. Flocculants include, for example, polyaluminum halides such as polyaluminum chloride (PAC), or the corresponding bromides, fluorides or iodides, polyaluminum silicates such as polyaluminum sulfosilicate (PASS) and water-soluble metal salts ( Aluminum chloride, aluminum nitrite, aluminum sulfate, potassium aluminum sulfate, calcium acetate, calcium chloride, calcium nitrite, calcium oxalate, calcium sulfate, magnesium acetate, magnesium nitrate, magnesium sulfate, zinc acetate, zinc nitrate, zinc sulfate, chloride Zinc, zinc bromide, magnesium bromide, copper chloride, copper sulfate), and combinations thereof. In some embodiments, the flocculant may be added to the mixture at a temperature below the glass transition temperature (Tg) of the resin.

  The particles may be agglomerated until a predetermined desired particle size is obtained. The predetermined desired particle size refers to the particle size that is desired to be obtained, as determined prior to production, and the particle size that is monitored during the growth process until such particle size is reached. Samples may be taken during the growth process and analyzed, for example, with a Coulter Counter for average particle size. Such agglomeration can be maintained at an elevated temperature while maintaining agitation or, if necessary, slowly raised to this temperature and held at this temperature for the time necessary to produce the desired particle size. However, it may be performed by obtaining aggregated particles. When a predetermined desired particle size is reached, a resin emulsion is added to grow the shell to give core-shell structured particles. The growth process is stopped by growing the shell until the desired core-shell toner particle size is reached, then adding the base (eg, NaOH) and then raising the pH of the reaction slurry by adding EDTA solution.

  After stopping the particle growth, the reaction mixture is heated to, for example, 85 ° C. to fuse the particles. The toner slurry is then cooled to room temperature, the toner particles are separated by sieving and filtration, then washed and lyophilized.

  The characteristics of the toner particles may be determined by any suitable technique and apparatus, as described in further detail below.

  The examples described herein below are illustrative of the different compositions and conditions that can be used when practicing this embodiment. All percentages are by weight unless otherwise indicated. However, this embodiment can be practiced with many types of compositions and may have many different uses in accordance with this disclosure above, as shown herein below. It will be clear.

  A low molecular crystalline organic compound and a low MW linear amorphous resin A (alkoxylated bisphenol A co-polyester containing fumaric acid, terephthalic acid and dodecenyl succinic acid) are separately melt-mixed to produce the above low molecular crystalline aromatics. A compatibility test of examples of resins binding diester compounds and amorphous polyester toners was observed. Melt mixing is performed on a hot plate at 150 ° C. for 20 minutes, then cooled and characterized by DSC. 1-3 give some examples of DSC plots. These plots are described in further detail below.

The aromatic diester used in the examples herein is di-tert-butylisophthalate of formula (6) (carbon to oxygen ratio of 4, melting point 83 ° C.). In the comparative examples, the following two other aromatic diesters are used. Isophthalic acid, diphenyl ester of formula (7) (carbon to oxygen ratio is 5, melting point is 138 ° C.)
And terephthalic acid, distearyl ester of formula (8) (carbon to oxygen ratio of 11, melting point 89 ° C.).

  The compatibility of these aromatic diesters and the linear amorphous polyester resin A was observed using DSC. The low molecular crystalline aromatic diester compound exhibits melting peaks at approximately 83 ° C., 138 ° C., and 89 ° C., respectively, and the linear amorphous resin A exhibits a glass transition temperature Tg at approximately 60 ° C. FIG. 1 is a DSC curve of melt-mixed di-tert-butyl isophthalate and linear amorphous polyester resin A. The Tg of Resin A dropped from about 60 ° C. to about 48.9 ° C., and no phase transition peak from the solid to the liquid of the crystalline compound was observed, indicating that di-tert-butyl isophthalate is a linear amorphous It is completely compatible with the polyester resin A. FIG. 2 is a DSC curve of melt-blended isophthalic acid, diphenyl ester and linear amorphous polyester resin A. The Tg of Resin A decreased from about 60 ° C. to about 46.4 ° C., and no phase transition peak from a solid to a liquid of a crystalline compound was observed, which means that isophthalic acid and diphenyl ester are linear amorphous polyester resins. It is completely compatible with A. FIG. 3 is a DSC curve of terephthalic acid, distearyl ester and linear amorphous polyester resin A melt-mixed. The crystallization enthalpy is greater than 20% of the original value of terephthalic acid distearyl ester, indicating that it is completely incompatible.

(Comparative Example 1)
(Preparation of toner composed of 15% isophthalic acid and diphenyl ester)
An overhead mixer was attached to a 2 liter glass reactor, to which 227.72 g of isophthalic acid and diphenyl ester dispersion (7.18 wt%, isophthalic acid diphenyl ester obtained from Sigma-Aldrich Chemical Company and 9% anionic surface activity ), 61.54 g of high Mw linear amorphous polyester resin B emulsion (35.22 wt%), 62.34 g of low Mw linear amorphous polyester resin A emulsion (34.84 wt%). %) 30.56 g of wax dispersion (wax available from International Group Inc., 30.19 wt%), 34.83 g of cyan pigment PB15: 3 (17.21 wt%). The linear amorphous resin B is a copolyester of alkoxylated bisphenol A with terephthalic acid and dodecenyl succinic acid. Separately, 3.58 g Al ₂ (SO 4) ₃ (27.85 wt%) was added as a flocculant while homogenizing at 3500 rpm. While stirring at 200 rpm, the mixture was heated to 40 ° C. to aggregate the particles. The particle size was monitored using a Coulter Counter until the core particles reached a volume average particle size of 4.35 microns, a GSD volume of 1.36, and then 40.55 g and 41.07 g of the A described above, respectively. A mixture of a resin emulsion and a B resin emulsion was added as a shell material to obtain core-shell structured particles having an average particle size of 6.21 microns and a GSD volume of 1.27. Thereafter, a 4 wt% NaOH solution was used, then 7.69 g EDTA (39 wt%) was used to raise the pH of the reaction slurry to 8.5 to freeze the toner growth. After freezing, the reaction mixture was heated to 85 ° C. and the toner particles were fused at 85 ° C. and pH 8.4. After fusing, the toner was rapidly cooled to obtain a final particle size of 7.66 microns, a GSD volume of 1.37, a GSD number of 1.35, and a roundness of 0.967. The toner slurry was then cooled to room temperature, screened (25 μm), separated by filtration, then washed and lyophilized.

(Comparative Example 2)
(Preparation of toner composed of 15% terephthalic acid and distearyl ester)
An overhead mixer is attached to a 2 liter glass reactor, which contains terephthalic acid, distearyl ester, high Mw linear amorphous resin A and low Mw linear amorphous resin B in a ratio of 15: 21.3: 21.3. Emulsion 488.12 g (12 wt%, prepared by co-emulsification), 30.15 g wax dispersion (wax available from International Group Inc., 30.19 wt%), 34.39 g cyan pigment PB15: 3 (17. 21 wt%) was added. Separately, 1.18 g of Al ₂ (SO 4) ₃ (27.85 wt%) was added as a floc forming agent while homogenizing at 3500 rpm. While stirring at 300 rpm, the mixture was heated to 38.2 ° C. to aggregate the particles. The particle size was monitored using a Coulter Counter until the core particles reached a volume average particle size of 5.25 microns, a GSD volume of 1.38, then 40.55 g and 40.03 g of the A described above, respectively. A mixture of a resin emulsion and a B resin emulsion was added as a shell material to obtain core-shell structured particles having an average particle size of 5.83 microns and a GSD volume of 1.23. Then, after using a 4 wt% NaOH solution, the pH of the reaction slurry was raised to 8 using 7.6 g EDTA (39 wt%) to freeze the toner growth. After freezing, the reaction mixture was heated to 85 ° C. and the toner particles were fused at 85 ° C. and pH 7. After fusing, the toner was rapidly cooled to obtain a final particle size of 6.41 microns, a GSD volume of 1.25, a GSD number of 1.31, and a roundness of 0.958. The toner slurry was then cooled to room temperature, screened (25 μm), separated by filtration, then washed and lyophilized.

Example 1
(Preparation of toner composed of 15% di-tert-butylisophthalate)
Attach an overhead mixer to a 2 liter glass reactor to which 417.33 g of di-tert-butylisophthalate dispersion (prepared by ball milling with 2.86 wt%, 9% anionic surfactant), 44.93 g of high Mw linear amorphous resin B emulsion (35.22 wt%), 45.51 g of low Mw linear amorphous resin A emulsion (A, 34.84 wt%), 22.31 g of wax dispersion ( Wax available from International Group Inc., 30.19 wt%), 25.43 g of cyan pigment PB15: 3 (17.21 wt%) was added. Separately, 2.62 g of Al ₂ (SO 4) ₃ (27.85 wt%) was added as a floc forming agent while homogenizing at 3500 rpm. While stirring at 200 rpm, the mixture was heated to 41.1 ° C. to aggregate the particles. The particle size was monitored using a Coulter Counter until the core particles reached a volume average particle size of 3.96 microns, a GSD volume of 1.26, then 29.60 g and 29.98 g of the A described above, respectively. A mixture of a resin emulsion and a B resin emulsion was added as a shell material to obtain core-shell structured particles having an average particle size of 6.48 microns and a GSD volume of 1.27. Thereafter, 4 wt% NaOH solution was used, and then the pH of the reaction slurry was raised to 7.8 using 5.62 g EDTA (39 wt%) to freeze the toner growth. After freezing, the reaction mixture was heated to 85 ° C. and the toner particles were fused at 85 ° C. and pH 8.4. After fusing, the toner was quenched to obtain a final particle size of 7.50 microns, a GSD volume of 1.31, a GSD number of 1.33, and a roundness of 0.960. The toner slurry was then cooled to room temperature, screened (25 μm), separated by filtration, then washed and lyophilized.

The toner of Example 1, Comparative Examples 1 and 2 and the control toner were evaluated using a Xerox® 700 Digital Color Press printer fusing device. Fused to Xerox® Color Xpressions® paper at 220 mm / s for gloss, MFT, cold offset performance, and thermal offset performance. The toner fusing performance is given in Tables 2 and 3. The control toner is a Xerox® 700 DCP toner containing a crystalline resin with a melting point of 65 ° C. to 85 ° C. and a Xerox® EA high gloss (such as used in a Xerox® DC250 printer). HG) toner. The fuser is a fusion device for the Xerox® 700 Digital Color Press printer.

  As shown in Table 2, the wrinkle fixing MFT of the toner containing isophthalic acid, diphenyl ester or terephthalic acid, distearyl ester is larger than the ULM EA control toner. The MFT of the control toner was 112 ° C., while the low molecular weight sample started at 117 ° C. and continued to 135 ° C. The two comparative toners containing low molecules did not give low melt properties.

In the case of isophthalic acid, diphenyl ester, as described above, it is compatible with the amorphous polyester resin, but the ratio of carbon to oxygen is 5 (for comparison, the carbon of amorphous polyester resins A and B to oxygen The melting point is 138 ° C., which is too high to melt the crystalline aromatic diester when fusing the toner. In the case of terephthalic acid and distearyl ester, the melting point is 83 ° C., but the hydrophobicity is too high, and the ratio of carbon to oxygen is 11, which becomes incompatible with the amorphous polyester resin as described above.

  As shown in Table 3, when di-tert-butylisophthalate is incorporated into the toner, a cold offset temperature (100 ° C. versus 129 ° C.) and wrinkle-fixed MFT (122 ° C.) for the Xerox® 700 DCP toner. In contrast, 111 ° C.) shifts to lower temperatures (the wrinkle fixed MFT value is accurate to approximately ± 3 ° C. or 4 ° C.). The speckle / thermal offset temperature was higher (210 ° C vs. 200 ° C), which resulted in a much greater degree of freedom of fusion (97 ° C vs. 71 ° C).

  The toner sample described above was blended with Xerox® 700 DCP additive and carrier to give a developer sample. Developer samples were allowed to equilibrate overnight in Zones A and J and then charged using a Turbula mixer for about 60 minutes. The A zone is a high humidity zone of about 28 ° C. and 85% relative humidity (RH), and the J zone is a low humidity zone of about 21 ° C. and RH 10%. Using a charge spectrophotometer using an electric field of 100 V / cm, the toner charge (Q / d) was measured and visually measured as the midpoint of the toner charge distribution. After removing the toner by blowing off with an air stream, the charge mass ratio (Q / m) of the toner was determined by a total charge blow-off method in which the charge on the ferrite cage remaining in the developer was measured. The total charge collected in the cage is calculated by dividing the weight of the cage before and after blow-off and dividing by the mass of toner removed by blow-off to obtain the Q / m ratio.

  The toner of Example 1 was tested and found to have a charge result that was acceptable and similar to that of a nominal ULM toner used as a control. In addition, the charging characteristics of the toner may be optimized, adjusting the thickness of the toner shell, changing the weight percentage of the crystalline material, incorporating low molecular crystalline aromatic diesters and crystalline polymers, optimizing the ratio, For example, both Q / m and Q / d may be improved by adjusting the toner aggregation / fusion process (eg, adjusting the fusing temperature).

  It will be appreciated that the various above disclosed features and functions or alternatives, other features and functions or alternatives may be desirably combined with many other systems or applications. In addition, various presently anticipated or anticipated alternatives, modifications, changes, or improvements may be subsequently made by those skilled in the art and are intended to be encompassed by the following claims.

Claims (6)

A polymer resin;
Wearing a coloring material and;
A low molecular crystalline aromatic diester having an aromatic core with a molecular weight of less than 1,000 g / mol , wherein the low molecular crystalline aromatic diester has the following formula:

A toner which is isophthalic acid, di-tert-butyl ester having   The toner according to claim 1, wherein the low molecular crystalline aromatic diester has a carbon to oxygen ratio of 3.5 to 6. 5. The toner according to claim 1, wherein the low molecular crystalline aromatic diester has a melting point of 60 ° C. or higher and 120 ° C. or lower . The toner according to any one of claims 1 to 3, wherein the polymer resin is an amorphous resin. Mixtures of amorphous polymer resins and low molecular crystalline aromatic diesters have a lower glass transition temperature than amorphous polymer resins, as determined by differential scanning calorimetry, and a noticeable transition from solid to liquid low molecular crystalline aromatic diesters. Characterized in that there is no phase transition peak and the fusion enthalpy of the low molecular crystalline aromatic diester in the mixture is measured to be less than 10% of the fusion enthalpy of the low molecular crystalline aromatic diester in pure form The toner according to claim 4 . The toner according to any one of claims 1 to 5 , wherein the polymer resin is a polyester resin.